TWI301490B - Catalyst composition and process for preparing norbornene-type homopolymers or copolymers - Google Patents
Catalyst composition and process for preparing norbornene-type homopolymers or copolymers Download PDFInfo
- Publication number
- TWI301490B TWI301490B TW091103634A TW91103634A TWI301490B TW I301490 B TWI301490 B TW I301490B TW 091103634 A TW091103634 A TW 091103634A TW 91103634 A TW91103634 A TW 91103634A TW I301490 B TWI301490 B TW I301490B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- catalyst composition
- product
- reaction
- add
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
Description
tt
1301490 發明背景 本發明有關於一種製備冰片烯型單聚物或共聚物之觸 媒°且β物’特別有關於一種使用原狀況（i n s i t u )觸媒組 合物以製備冰片烯單聚物或共聚物的方法。 冰片烯型聚合物（p〇lynorb〇rnenes)具有耐高溫和高 透明性的材料特性’而具特殊官能基的冰片烯型聚合物更 f有光電產品之應用價值。因此開發適用於合成冰片烯型 單聚物或共聚物之觸媒，為一重要之課題。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a catalyst for preparing a norbornene type monomer or copolymer, and the beta material is particularly useful in the preparation of a norbornene monomer or copolymer using an in situ catalyst composition. Methods. The borneol-type polymer (p〇lynorb〇rnenes) has a material property of high temperature resistance and high transparency, and the norbornene type polymer having a special functional group has an application value of an optoelectronic product. Therefore, development of a catalyst suitable for synthesizing a borneol type monomer or copolymer is an important subject.
已有許多研究者使用不同的金屬觸媒來合成冰片稀型 聚合物。例如，Goodal 1等人在U. S. Patent No. 5，468,819 中使用[ally卜Ni-COD ]+( weakly coordinating anion)，其中c〇D = cyclooctadiene (環辛二烯）。Upian 等人在 WO 00/20472 中使用[(R，）zM(L，）x(L")y]b[WCA]d，其 中[(R )ZM(L )x(Ln)y]為陽離子錯合物，m為第l〇族過渡金 屬；R’為含陰離子型含碳氫基之配位子；L，為第15族之中 性電子施者配位子；L ’’為1 a b i 1 e之中性電子施者配位子； X為1或2 ;y為〇， 1， 2，或3 ;z為0或1，其中X，y，和z之 和為4，[WCA]為弱配位之counteranion complex ;b 和d 為Many researchers have used different metal catalysts to synthesize borneol thin polymers. For example, Goodal 1 et al., U.S. Patent No. 5,468,819, uses [ally, Ni-COD ] + (lessly coordinating anion), wherein c 〇 D = cyclooctadiene (cyclooctadiene). Upian et al. used [(R,)zM(L,)x(L")y]b[WCA]d in WO 00/20472, where [(R )ZM(L )x(Ln)y] is a cation a complex, m is a transition metal of the 1st group; R' is a ligand containing an anionic hydrocarbon-containing group; L is a group 15 neutral electron donor ligand; L '' is 1 abi 1 e Neutral electron donor ligand; X is 1 or 2; y is 〇, 1, 2, or 3; z is 0 or 1, where the sum of X, y, and z is 4, [WCA] a counteranion complex for weak coordination; b and d are
平衡陽離子錯合物和[WCA]的數目。具體的例子為（ai i)Balance the number of cation complexes and [WCA]. The specific example is (ai i)
palladium(tricyclohexylphosphine)triflate 。 Sen 等人 在 WO 0 1 /2 1 670 中使用（L)2Pd(R)(X)和L，Pd(R)(X)，其中L 為單芽團磷或氮配位子，L，為雙芽團磷或氮配位子，χ為 陰離子基團，R為烷基或芳香基（aryl)。具體的例子為 (PPh3)2Pd(CH3)(Br)。Palladium (tricyclohexylphosphine) triflate. Sen et al. used (L)2Pd(R)(X) and L, Pd(R)(X) in WO 0 1 /2 1 670, where L is a single bud phosphorus or nitrogen ligand, L, A double bud phosphorus or nitrogen ligand, χ is an anionic group, and R is an alkyl group or an aryl group. A specific example is (PPh3)2Pd(CH3)(Br).
0424-7258TWF;02900035;Ca t hy.p t d 第6頁 1301490 五、發明說明（2) 然而，上述專利中所使用之觸媒為各項八 應產物，需經過分離觸媒的步驟，非常麻煩。份所得之反 發明之目的及概述 因此，本發明之目的即為開發出一種製備 聚物或共聚物之觸媒組合物，此觸媒組合物係_片稀型單 之混合狀態，而非各成份反應所得產物之分離二=各成份 本發明之另一目的為提供一種製備冰片烯型=变铷 共聚物之方法，其係使用上述之觸媒組合物，在$物或 (in situ)下直接合成冰片烯聚合物。由於此觸媒'ϋ 不需分離出來，而可以在原狀況（in situ)下直接#=物 因此步驟簡單，可節省費用。 使用， 本發明之另一目的為提供一種觸媒產物，复可用 備冰片婦型單聚物《共聚4匆。本發明纟提供使用此觸= 物以製備冰片烯單聚物或共聚物的方法。 、 人从ί 了達成本發明之上述目的，本發明之第一種觸媒组 j包括下列成份：⑷-過渡金屬化合物Ml4，其中“ _ 第10，，屬，L為中性電子施者配位子；（b)含有雙鍵或三 鍵之奴氫基鹵素；以及（C)含有可取代與金屬鍵結之鹵素 的非配位或弱配位陰離子之鹽類，其中此觸媒組合物係處 於成份（a)、（b)、（c)之混合狀態，或處於成份（aM〇(b) 之反應產物與成份（c)之混合狀態下，或處於成份（a)和 (C )之混合狀態下。 本發明之第二種觸媒組合物包括下列成份：（a) 一過0424-7258TWF; 02900035; Ca t hy.p t d Page 6 1301490 V. INSTRUCTIONS (2) However, the catalyst used in the above patent is a product of eight kinds of products, which requires a step of separating the catalyst, which is very troublesome. OBJECTS AND SUMMARY OF THE RESULTS OF THE INVENTION Accordingly, it is an object of the present invention to develop a catalyst composition for preparing a polymer or a copolymer which is in a mixed state of a thin sheet, rather than each Separation of the product obtained by the reaction of the components = each component Another object of the present invention is to provide a process for preparing a borneol-type = ruthenium-based copolymer using the above-mentioned catalyst composition at or under the in situ Direct synthesis of borneol polymers. Since the catalyst 'ϋ does not need to be separated, it can be directly in the original condition (in situ). Therefore, the steps are simple and the cost can be saved. In use, another object of the present invention is to provide a catalyst product which can be used in the preparation of a borne wafer type monomer. The present invention provides a method of using this tactile to prepare a norbornene monomer or copolymer. The first catalyst group j of the present invention comprises the following components: (4)-transition metal compound M14, wherein "_10, genus, L is a neutral electron donor. a (b) a hydrogen-containing halogen containing a double bond or a triple bond; and (C) a salt containing a non-coordinating or weakly coordinating anion capable of substituting a metal-bonded halogen, wherein the catalyst composition Is in the mixed state of components (a), (b), (c), or in the mixed state of the component (aM〇(b) reaction product and component (c), or in components (a) and (C) In the mixed state, the second catalyst composition of the present invention comprises the following components: (a)
1301490 五、發明說明（3) 渡金屬化合物M l ，宜中μ糸筮〗 者配位子；4弟10紅金屬，L為中性電子施 弱配位陰離子之3Λ 與金屬鍵結之自素的非配位或 # ^ ^ ifn r J"類，以及（e )含鹵素之溶劑，其中該觸 媒組：：係處於成份(a)、(c)、(e)之混合狀態；。1301490 V. INSTRUCTIONS (3) Metal compound M l , Yizhong μ糸筮〗 The person with a seat; 4 brother 10 red metal, L is a neutral electron weakening coordination anion 3Λ and metal bond self-prime a non-coordinating or #^^ ifn r J" class, and (e) a halogen-containing solvent, wherein the catalyst group: is in a mixed state of components (a), (c), (e);
Situ)以制供i U 觸媒合物均可在原狀況下（in 以衣備冰片烯型單聚物或共聚苴 觸媒組合物之在太T取人 ， 八万法為 在 人物tffl 在下聚5至父一冰片烯型單體，此觸媒組 口物之用里可為單體之0 〇2至〇 2莫耳％。Situ) can be used in the production of i U catalysts in the original conditions (in the preparation of the norbornene type monomer or copolymerization catalyst composition in the T to take people, 80,000 method in the character tffl in the lower 5 to the parent-bornee-type monomer, the catalyst medium can be used as a monomer of 0 〇2 to 〇2 mol%.
本發明之觸媒產物為下列成份之反應過 金屬鍵結之函辛3的有非二配鍵位之二氫基W;(C)含有可取代與 ,,,μ ®常的非配位或弱配位陰離子之鹽類；以及 (d) 一貝子提供者，其可與eta_3_炔丙基反應。 圖式之簡單說明 第1圖顯不依據本發明實施例3至5以合成本發明觸媒 產物之反應式。 發明之詳細敘述The catalyst product of the present invention is a dihydrogen group W having a non-di-bonding position of a metal-bonded functional group of the following components; (C) containing a non-coordinating or a salt of a weakly coordinating anion; and (d) a shellfish donor which is reactive with eta_3_propargyl. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a reaction formula for synthesizing the catalyst product of the present invention in accordance with Examples 3 to 5 of the present invention. Detailed description of the invention
、本發明一共開發出兩種觸媒組合物和一種觸媒產物， 都適合於製備士片烯（norbornene)型單聚物或共聚物。 、本發明之第—種觸媒組合物包括下列成份：（a) 一過 渡金屬化合物ML4，其中M為第丨〇族金屬，L為中性電子施 者配位子；（b)含有雙鍵或三鍵之碳氫基鹵素；以及&》含The present invention has developed two catalyst compositions and one catalyst product, both of which are suitable for the preparation of norbornene type monomers or copolymers. The first catalyst composition of the present invention comprises the following components: (a) a transition metal compound ML4, wherein M is a steroidal metal, L is a neutral electron donor ligand; (b) contains a double bond. Or a three-bonded hydrocarbon-based halogen; and &
0424-7258TWF;0290003 5;Ca t hy.P t d 第8頁 13014900424-7258TWF;0290003 5;Ca t hy.P t d Page 8 1301490
有可取代與金屬鍵結之函素 類。此觸媒組合物係處於成 下’或處於成份（a)和（b)之 態下。 的非配位或弱配位陰離子之鹽 份（a)、（ b)、（ c )之混合狀態 反應產物與成份（c )之混合狀 .上述本發明之第一種觸媒組合物可用於在原狀況 s 1 tu)下以製備冰片烯型單聚物“ έ日人‘ A取A 卞4 /、乂物，在苐一種觸媒 、、且合物之存在下聚合至少一冰月嬌】罝妒 田旦π达π触田旦 不片肺型早體。觸媒組合物之 里可為早體用里之〇· 02至〇· 2莫耳％。所謂的原狀況下，There are classes of elements that can be substituted with metal bonds. The catalyst composition is under or in the presence of components (a) and (b). a mixture of the mixed state product of the non-coordinating or weakly coordinating anion (a), (b), (c) and the component (c). The first catalyst composition of the present invention described above can be used for In the original condition s 1 tu) to prepare a norbornene type monomer "έ日人' A take A 卞 4 /, 乂, in the presence of a catalyst, and the presence of a compound to polymerize at least one ice moon Jiao]罝妒田旦 π达π Touch Tiandan is not a lung type early body. The catalyst composition can be used in the early body 〇·02 to 〇· 2 mol%. Under the original condition,
亦即本發明之卜種觸媒組合物不需先行純化分離，而可 在各成份混合狀態下直接與單體聚合。所謂的混合狀態， 可為成份（a)、（b)、（C)處於混合狀態。或者，成份和 (b)可先行反應，所得之產物再於成份（c)混合之混合狀 態0 本發明之過渡金屬化合物ML4中，L可為三苯基膦That is, the catalyst composition of the present invention can be directly polymerized with the monomer in a mixed state without the need for purification and separation. In the so-called mixed state, the components (a), (b), and (C) may be in a mixed state. Alternatively, the component and (b) may be reacted first, and the obtained product is further mixed with the component (c). In the transition metal compound ML4 of the present invention, L may be triphenylphosphine.
(PPh3，triphenylphosphine)、（PCy3， tricyclohexylphosphine), (P(o-tol)3， trio-tolylphosphine)，較佳者為PPh3 °ML4之具體例子包 括Pd(PPh3)4 (tetrakis(triphenylphosphine) palladium (0)), Ni(PPh3)4(tetrakis (triphenylphosphine)nickel(O)), Pt(PPh3)4 (tetrakis(triphenylphosphine)platium(O)) ’ 較佳之例 子為Pd(PPh3)4。 本發明上述含有可取代與金屬鍵結之_素的非配位或 弱配位陰離子之鹽類可為鹼金屬（如鋰）之鹽類，或銀之鹽(PPh3, triphenylphosphine), (PCy3, tricyclohexylphosphine), (P(o-tol)3, trio-tolylphosphine), preferred examples of PPh3 °ML4 include Pd(PPh3)4 (tetrakis(triphenylphosphine) palladium (0 )), Ni(PPh3)4(tetrakis(triphenylphosphine)nickel(O)), Pt(PPh3)4(tetrakis(triphenylphosphine)platium(O))' A preferred example is Pd(PPh3)4. The above-mentioned salt containing a non-coordinating or weakly coordinating anion capable of substituting a metal-bonded ketone may be a salt of an alkali metal (e.g., lithium) or a salt of silver.
0424-7258TWF;02900035;Cathy.ptd 第9頁0424-7258TWF; 02900035; Cathy.ptd Page 9
1301490 五、發明說明（5) 類’較佳者為銀鹽。非配位或弱配位陰離子可為BF4—， PFV，CF3so3-，SbF6-，B(C6F5)4-，b[c6h3(cf3)2]4-，no3—，和1301490 V. INSTRUCTIONS (5) Class 'Better is silver salt. The non-coordinating or weakly coordinating anions may be BF4-, PFV, CF3so3-, SbF6-, B(C6F5)4-, b[c6h3(cf3)2]4-, no3-, and
Cicocr。較佳之可取代與金屬鍵結之鹵素的非配位或弱配 位陰離子之鹽類的例子包括AgBF4，AgSbF6，LiB(C6F5)4， 硝酸銀（siliver nitrate)和醋酸銀（silver acetate) 等。 本發明含有雙鍵或三鍵之碳氫基鹵素可與過渡金屬化 合物ML4進行反應。當此碳氫基_素包括雙鍵時，其具體 例子包括CH3CH = CHCH2C1、CH2 = CCH3CH2C1、CH2 = CHCHCH3C1、 等，較佳者為CH3CH = CHCH2C1。當此碳氫基鹵素 包括二鍵時，具體例子包括快丙基溴（propargyl bromide ;HCCCH2Br)、H3CCCCH2Br (卜bromo-2-butyne) 等，較佳者為炔丙基漠（propargyl bromide ;HCCCH2Br) 和H3CCCCH2Br。 對於本發明之第一種觸媒組合物，當碳氫基_素包括 二鍵時’此第一種觸媒組合物可更包括成份（d) 一質子提 供者’其可與eta —3 —炔丙基反應，是具有質子/hydride活 性基之親核性（nucleophi丨ic)基團或化合物。此質子提供 者可為胺類，其具體例子包括H2NCH2CH2NH2、hN(C2h5)2，較 佳者為H2NCH2CH2NH2。 、 本發明之第二種觸媒組合物包括下列成份：（a) —過 渡金屬化合物ML4，其中Μ為第1 〇族金屬，L·為中性電子施 者配位子；（c)含有可取代與金屬鍵結之鹵素的非配位或 弱配位陰離子之鹽類；以及（e)含鹵素之溶劑；其中此觸Cicocr. Examples of the salt which may preferably be substituted with a metal-bonded halogen non-coordinating or weakly coordinating anion include AgBF4, AgSbF6, LiB(C6F5)4, silver nitrate and silver acetate. The hydrocarbon-based halogen containing a double bond or a triple bond of the present invention can be reacted with the transition metal compound ML4. When the hydrocarbon group includes a double bond, specific examples thereof include CH3CH = CHCH2C1, CH2 = CCH3CH2C1, CH2 = CHCHCH3C1, and the like, and preferably CH3CH = CHCH2C1. When the hydrocarbon-based halogen includes a double bond, specific examples include propargyl bromide (HCCCH2Br), H3CCCCH2Br (bromo-2-butyne), and the like, preferably propargyl bromide (HCCCH2Br). And H3CCCCH2Br. For the first catalyst composition of the present invention, when the hydrocarbon group includes a double bond, the first catalyst composition may further comprise a component (d) a proton donor 'which may be associated with eta-3 The propargyl reaction is a nucleophi丨ic group or compound having a proton/hydride active group. The proton donor may be an amine, and specific examples thereof include H2NCH2CH2NH2, hN(C2h5)2, and more preferably H2NCH2CH2NH2. The second catalyst composition of the present invention comprises the following components: (a) a transition metal compound ML4, wherein ruthenium is a first steroidal metal, L. is a neutral electron donor ligand; (c) a salt that replaces a non-coordinating or weakly coordinating anion of a metal-bonded halogen; and (e) a halogen-containing solvent;
上述本發明> # _ s i ) ΠΓ ,ν制弟二種觸媒組合物可用於在原狀況（i η 组人 户衣/片烯型單聚物或共聚物，在第二種觸媒 用Γ聚合至少一冰片烯型單體。觸媒組合物之 體用量之〇.〇2至〇2莫耳％。所謂的原狀況下， f :本：第二種觸媒組合物不需先行純化分離，而可 成伤a) (c)、（ e)混合狀態下直接與單體聚合。 本發明之上述第一種或第二種觸媒組合物可更包栝一 施者清除劑（d〇n〇r scavenger)，以用來除去殘餘之過渡 金屬化合物ML4，以使觸媒之活性提高。施者清除劑之具 體例子包括B(C6H5)3，Ni(COD)2，CuCl 等。 本發明之觸媒產物為下列成份之反應產物：（a) 一過 渡金屬化合物ML*，其中μ為第1 〇族金屬，[為中性電子施 者配位子；（b)含有三鍵之碳氫基鹵素；（c)含有可取代與 金屬鍵結之鹵素的非配位或弱配位陰離子之鹽類；以及 (d) —質子提供者，其可與eta-3 —炔丙基反應。 為了使得本發明之内容更容易瞭解，以下將一具體例 子以說明合成本發明觸媒產物的反應。當上述過渡金屬化 合物Mb為Pd (PPhs)4，含有三鍵之碳氫基鹵素為 IC C C CIB r ’含有可取代與金屬鍵結之_素的非配位或弱 配位陰離子之鹽類為AgBF4，質子提供者為H2NCH2CH2NH2 時’其合成反應式如第1圖所示，實際之反應步驟如以下The above-mentioned present invention ># _ si ) ΠΓ , ν 弟 two kinds of catalyst composition can be used in the original condition (i η group of household clothes / ene terene type monomer or copolymer, in the second catalyst Γ Polymerizing at least one borneol-type monomer. The amount of the catalyst composition is from 〇2 to 〇2 mol%. In the so-called original condition, f: this: the second catalyst composition does not need to be purified first. And can be injured a) (c), (e) in the mixed state directly with the monomer polymerization. The above first or second catalyst composition of the present invention may further comprise a scavenger (d〇n〇r scavenger) for removing residual transition metal compound ML4 to activate the catalyst. improve. Specific examples of the donor scavenger include B(C6H5)3, Ni(COD)2, CuCl, and the like. The catalyst product of the present invention is a reaction product of the following components: (a) a transition metal compound ML*, wherein μ is a Group 1 metal, [is a neutral electron donor ligand; (b) contains a triple bond. a hydrocarbon-based halogen; (c) a salt containing a non-coordinating or weakly coordinating anion capable of substituting a metal-bonded halogen; and (d) a proton donor which is reactive with an eta-3-propargyl group . In order to make the content of the present invention easier to understand, a specific example will be given below to illustrate the reaction for synthesizing the catalyst product of the present invention. When the above transition metal compound Mb is Pd(PPhs)4, the hydrocarbon having a triple bond is a compound having a non-coordinating or weakly coordinating anion which can be substituted with a metal bond. AgBF4, when the proton donor is H2NCH2CH2NH2, the synthesis reaction formula is as shown in Fig. 1, and the actual reaction steps are as follows:
13014901301490
个贯明上迹ι乐一、二種觸媒組人 合於用來聚合至少一冰片烯型單體，σ〜和觸媒產物均適 物或共聚物。適用於本發明之冰片烯到冰片烯型單聚 可為冰片稀或冰片烯衍生物。冰片 〜體並；又有限制， NB-Si(〇Me)3 [5-(bicycloheptenyl)订生物的具體例子如 trimethoxysilane] 〇 依據本發明’彳聚合兩種不同之 到冰片烯型共聚物。例…發明上述之第—早：種：： 組合物和觸媒產物可用來聚合冰片烯和NB_si(〇Me)。 依據本發明，可聚合一冰片烯型單體和一不同3於 ，之單體。例士口 ’本發明上述之第一、二種觸媒組合物和 觸媒產物可用來聚合一冰片烯型單體和一丙烯酸類。適用 之丙烯酸類例如丙烯酸t- 丁酯（t-BA ; t-buty 1 acrylate)、甲基丙烯酸丁酯（bma ;butyl methacrylate)、和丙烯酸甲酯（Ma ; methyl acrylate)。 以下藉由數個實施例以更進一步說明本發明之方法、 特徵及優點’但並非用來限制本發明之範圍，本發明之範 圍應以所附之申請專利範圍為準。 製備觸媒組合物 實施例1 : ?(1(下？比）4合成方法 取5 g 的 PdCl2 (28.2 mmol)和 37 g 的 PPh3(141 mmol)One of the two types of catalysts is used to polymerize at least one borneol-type monomer, and σ~ and the catalyst product are both suitable or copolymer. The norbornene to norbornene type monopolymer suitable for use in the present invention may be a borneol thin or a norbornene derivative. Borneol ~ body; and there are limitations, NB-Si (〇Me) 3 [5-(bicycloheptenyl) specific examples of organisms such as trimethoxysilane] 〇 According to the invention, 彳 polymerization of two different types of copolymers to the borneol type. EXAMPLES OF THE INVENTION The above-mentioned first-earth: species:: The composition and the catalyst product can be used to polymerize borneol and NB_si (〇Me). According to the present invention, a borneol-type monomer and a different monomer can be polymerized. The above first and second catalyst compositions and catalyst products of the present invention can be used to polymerize a borneol-type monomer and an acrylic acid. Suitable acrylics are, for example, t-buty 1 acrylate, butyl methacrylate, and methyl acrylate. The invention is not limited by the scope of the appended claims, but the scope of the invention is intended to be limited by the scope of the appended claims. Preparation of Catalyst Composition Example 1: ?(1 (down ratio) 4 synthesis method Take 5 g of PdCl2 (28.2 mmol) and 37 g of PPh3 (141 mmol)
0424-7258TWF;02900035;Ca t hy.pt d 第12頁 1301490 五、發明說明（8) 置於DMSO( 20 0 mL)溶劑内，加熱到140 °C溶解，待完全溶 解後停止加熱，1 5分鐘後再加入Η2 Ν Ν Η2 · H2 0 ( 6 m 1 )，授拌 至室溫，再使用無氧快速過濾器，快速過濾，以乙醇和乙 醚各洗產物二次，過濾抽乾，可得黃色粉末固體Pd(PPh3) 4(31 g ;Yield =95 %) 〇 實施例2 : Pd(PPh3)2(Br)( W-CHCCIU 合成方法0424-7258TWF; 02900035; Ca t hy.pt d Page 12 1301490 V. Description of the invention (8) Place in DMSO (20 mL) solvent, heat to 140 °C to dissolve, stop heating after completely dissolved, 1 5 After a minute, add Η2 Ν Ν Η2 · H2 0 (6 m 1 ), stir to room temperature, then use an anaerobic fast filter, filter quickly, wash the product twice with ethanol and ether, filter and drain, get Yellow powder solid Pd(PPh3) 4 (31 g; Yield = 95%) 〇 Example 2: Pd(PPh3)2(Br) (W-CHCCIU synthesis method
將由實施例1所得之Pd(PPh3)4(5g，4· 3mmol)溶於苯溶 劑（50 mL)内，再加入快丙基溴（propargyl bromide) (〇. 8g，6.7mmol)於室溫下攪拌反應30分鐘，待反應完後經減 壓濃縮抽掉大部分的溶劑，再緩慢加入乙醚使產物沉析出 來，過濾可得土黃色固體？(1(??}13)2(81〇(7?1-(：11(：(：112)(2.8 g ; Yield = 87%)。 實施例3 : Pd(PPh3)2(Br)[ T^-CUejCCiy 合成方法 將由實施例1所得之Pd( PPh3 )4 (1 g，0 · 86mmo 1)溶於苯 溶劑（20 mL)内，再加入 MeCCCH2Br(0.23g， 1.73mmol)室 溫下攪拌反應3 0分鐘，反應完後經減壓濃縮抽掉大部分的 溶劑，再緩慢加入乙醚使產物沉析出來，過濾可得土黃色 固體Pd(PPh3)2(Br)( 771 -CH2CCMe)/Pd(PPh3)2(Br)[ 7?1 -C(Me)CCH2](0· 5g ; Yield = 76%)。 實施例3至5之反應式如第1圖所示。 實施例4 : [Pd(PPh3)2( ??3-CH2CCMe)]BF4 合成方法The Pd(PPh3)4 (5 g, 4.3 mmol) obtained in Example 1 was dissolved in a benzene solvent (50 mL), and then added to a solution of propargyl bromide (〇. 8 g, 6.7 mmol) at room temperature. The reaction was stirred for 30 minutes. After the reaction was completed, most of the solvent was removed by concentration under reduced pressure, and then diethyl ether was slowly added to precipitate the product. (1(??}13)2(81〇(7?1-(:11(:::112)(2.8 g; Yield = 87%). Example 3: Pd(PPh3)2(Br)[T ^-CUejCCiy Synthetic Method Pd(PPh3)4 (1 g, 0 · 86mmo 1) obtained in Example 1 was dissolved in benzene solvent (20 mL), and then added to MeCCCH2Br (0.23 g, 1.73 mmol) at room temperature. After 30 minutes, after the reaction was completed, most of the solvent was concentrated under reduced pressure, and then diethyl ether was slowly added to precipitate the product, and filtered to obtain a pale yellow solid Pd(PPh3)2(Br)( 771 -CH2CCMe)/Pd ( PPh3) 2 (Br) [ 7 ? 1 -C(Me) CCH 2 ] (0.5 g; Yield = 76%). The reaction formulas of Examples 3 to 5 are shown in Fig. 1. Example 4: [Pd( PPh3)2(??3-CH2CCMe)]BF4 synthesis method
0424-7258TWF;02900035;Ca t hy.p t d 第13頁 1301490 五、發明說明（9) 將由實施例3所得之？4(??113)2〇1')(7?1-(：112(^^^)/0424-7258TWF; 02900035; Ca t hy.p t d Page 13 1301490 V. Description of Invention (9) What will be obtained from Example 3? 4(??113)2〇1')(7?1-(:112(^^^)/
Pd(PPh3)2(Br)[ 7/1- C(Me)CCH2](0.44g，〇.57mmol)溶於 CH2C12 溶劑（20 mL)内，再加入 AgBF4(〇.llg，〇·57ππηο1)， 即產生土白色AgBr沉澱，攪拌15分鐘後過濾掉固體AgBr， 濾液再經減壓濃縮抽掉大部分的溶劑，再緩慢加入乙醚使 產物沉析出來，過濾可得灰白色固體^以”匕^”3- CH2CCMe)]BF4(0.34g ; Yield =77 %)。 實施例5 : [Pd(PPh3)2( τ?3-CH2C(CHMe)(NHCH2-))]2(BF4)2 合 成方法 將由實施例4 所得之[Pd(PPh3)2( a3-CH2CCMe) ]BF4 (0· lg，0.13mniol)溶於 CH2C12 溶劑（15 mL)内，於-35°C 下加入 H2NCH2CH2NH2(4mg，0.06 5mmol)，攪拌30 分鐘後，經減壓濃 縮抽掉大部分的溶劑，再緩慢加入乙醚使產物沉析出來， 過濾可得土白色固體[Pd(PPh3)2( 773-CH2C(CMe) (NHCH2-))]2(BF4)2(0.16g ; Yield = 75%)。 實施例6 : [Pd(PPh3)2( 773-CH2C(NEt2)(CHMe))]SbF6 合成方 法 進行如實施例4所述之相同步驟，但將以AgSbF6取代 AgBF4，即可得到[Pd(PPh3)2(h3-CH2CCMe)]SbF6。 將[Pd(PPh3)2( 773-CH2CCMe)]SbF6(0· 5g，0· 5 66mmol) 溶於CH2C12溶劑（20 mL)内，於-35 t下加入過量的 HNEt2(0.2g，2.74mmol)，攪拌30分鐘後，經減壓濃縮抽Pd(PPh3)2(Br)[ 7/1- C(Me)CCH2](0.44g, 〇.57mmol) was dissolved in CH2C12 solvent (20 mL), then added with AgBF4 (〇.llg, 〇·57ππηο1), That is, a white AgBr precipitate is produced, and after stirring for 15 minutes, the solid AgBr is filtered off, and the filtrate is concentrated under reduced pressure to remove most of the solvent, and then the ether is slowly added to precipitate the product, and the mixture is filtered to obtain an off-white solid. 3-CH2CCMe)]BF4 (0.34 g; Yield = 77%). Example 5: [Pd(PPh3)2( τ?3-CH2C(CHMe)(NHCH2-)) 2 (BF4) 2 Synthesis Method [Pd(PPh3)2( a3-CH2CCMe)] obtained from Example 4 BF4 (0· lg, 0.13mniol) was dissolved in CH2C12 solvent (15 mL), H2NCH2CH2NH2 (4 mg, 0.06 5 mmol) was added at -35 ° C, and after stirring for 30 minutes, most of the solvent was removed by concentration under reduced pressure. Further, diethyl ether was slowly added to precipitate the product, which was filtered to give a white solid [Pd(PPh3)2( 773-CH2C(CMe)(NHCH2-)) 2 (BF4) 2 (0.16 g; Yield = 75%). Example 6: [Pd(PPh3)2( 773-CH2C(NEt2)(CHMe))]SbF6 Synthesis method The same procedure as described in Example 4 was carried out, but AgBF4 was replaced by AgSbF6 to obtain [Pd(PPh3). ) 2 (h3-CH2CCMe)] SbF6. [Pd(PPh3)2( 773-CH2CCMe)]SbF6 (0·5g, 0·5 66mmol) was dissolved in CH2C12 solvent (20 mL), and excess HNEt2 (0.2 g, 2.74 mmol) was added at -35 t After stirring for 30 minutes, concentrated and concentrated under reduced pressure
0424-7258TWF;02900035;Ca t hy.p t d 第14頁 1301490 五、發明說明（10) 掉大部分的溶劑，再緩慢加入乙醚使產物沉析出來，過濾 可得土白色固體[Pd(PPh3)2( 773_CH2C(NEt2)(CHMe))]SbF6 (〇.34g ;Yield = 61%)。 冰片烯型單聚物和共聚物之合成 冰片烯之單聚： 實施例7 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt°/〇)4mL 。 二、 觸媒 1·將實施例2所得之觸媒Pd(PPh3)2(Br)( W-CHCCIU秤 ◦ •0 36g( 0.048mmol)置入 20mL sample vial，加入 3mL 之 CH2C12，使溶解之。 2·秤0. 016g(0· 082mmol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。並攪拌2 0 m i η後，注入步驟一中，開始反 _ 應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之’將 產物置於烘箱中隔夜烘乾，秤重〇 · 8 1 g。 實施例8 進行和實施例7相同的步驟，但將AgBF4改為0· 085 g0424-7258TWF; 02900035; Ca t hy.ptd Page 14 1301490 V. INSTRUCTIONS (10) Most of the solvent is removed, and then the ether is slowly added to precipitate the product, and the white solid is obtained by filtration [Pd(PPh3)2 (773_CH2C(NEt2)(CHMe))]SbF6 (〇.34g; Yield = 61%). Synthesis of borneol-type monomer and copolymer Monomerization of borneol: Example 7 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt °/〇) 4 mL. 2. Catalyst 1. The catalyst Pd(PPh3)2(Br) obtained in Example 2 (W-CHCCIU scale • 0 36 g (0.048 mmol) was placed in 20 mL sample vial, and 3 mL of CH2C12 was added to dissolve. 2·Weighing 0. 016g (0· 082mmol) of AgBF4 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, add it to the catalyst in step 1 by pipetting, and stir 20 μm η, then inject In the first step, the reaction was started. 3. After the reaction was completed, MeOH was added to precipitate, and then filtered. The product was placed in an oven and dried overnight, weighing 〇·8 1 g. Example 8 The same procedure as in Example 7, but changing AgBF4 to 0·085 g
0424-7258TWF;02900035;Ca t hy.P t d 第15頁 1301490 五、發明說明（11) (0.25 mmol )之AgSbF6，溶劑改用 C6H5C1 。產物為2· 28 g 〇 實施例9 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·將實施例2所得之觸媒Pd(PPh3)2(Br)( W-CHCCIU* 0. 009g(0.012mmol)置入20mL sample vial，加入3mL 之 C6 H5 C 1，使溶解之。 2. 秤0· 007g(0· 02mmol)之AgSbF6 置入5mL sample v i a 1，加入2 m L之C6 H5 C1，使溶解之，用滴管吸取加入步驟 1. 中之觸媒，並攪拌40 min。 3. 秤(K 0 0 6g( 0.022mmol)之 Ni(C0D)2 置入 5mL sample vial，加入2mL之toluene，使溶解之，再加入步驟2·中。 授拌5 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾、之，將 產物置於烘箱中隔夜烘乾，秤重0. 2 3g。 實施例1 0 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 。 二、 觸媒0424-7258TWF; 02900035; Ca t hy.P t d Page 15 1301490 V. Inventive Note (11) (0.25 mmol) of AgSbF6, solvent changed to C6H5C1. The product was 2·28 g 〇 Example 9 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · The contact obtained in Example 2 The medium Pd(PPh3)2(Br) (W-CHCCIU* 0. 009g (0.012mmol) was placed in 20mL sample vial, and 3mL of C6 H5 C1 was added to dissolve it. 2. Scale 0· 007g (0·02mmol) Place AgSbF6 in 5 mL sample via 1, add 2 m L of C6 H5 C1, dissolve it, add to the catalyst in step 1. with a pipette and stir for 40 min. 3. Scale (K 0 0 6g ( 0.022 Add mmol of Ni(C0D)2 into 5mL sample vial, add 2mL of toluene, dissolve it, and add it to step 2. · After mixing 5 mi η, inject into step one and start the reaction. After the product was added, MeOH was allowed to settle, and then filtered, and the product was placed in an oven overnight to dryness, weighing 0. 2 3 g. Example 1 0. Monomer pretreatment In a 50 mL reaction flask, degas purification Toluene 20mL and norbornene (85 wt%) 4mL.
0424-7258TWF;02900035;Ca t hy.p t d 第16頁 1301490 五、發明說明（12) 1·將實施例2所得之觸媒Pd(PPh3)2(Br)( W-CHCCI^)秤 0.009g(0.012mmol)置入20mL sample vial，加入3mL 之 CH2C 12，使溶解之。 2.秤0· 004g(0. 021mmol)之AgBF4 置入5mL sample v i a 1，加入2mL之CH2C 12，使溶解之，用滴管吸取加入步驟 1·中之觸媒，並攪拌40 min。 3·秤0.005g(0.051mmol)之CuCl 置入5mL sample vial，加入lmL之CH2C12，使溶解之，再加入步驟2·中，攪 拌1 0 m i η後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 06g。 實施例11 一、 單體前處理 在5 0mL之反應瓶中，degas純化之to 1 uene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·將實施例3所得之觸媒Pd(PPh3) 2(Br)[ 7?1-C(Me)CCH2]秤0· 03 7g(0· 048mmol)置入2 0mL sample vial，加入 3mL 之 C6H5C1，使溶解之。 2·秤0· 0 28g(0· 081mmol)之AgSbF6 置入5mL sample v i a 1，加入2 m L之C6 H5 C 1，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將0424-7258TWF; 02900035; Ca t hy.ptd Page 16 1301490 V. Description of Invention (12) 1. The catalyst Pd(PPh3)2(Br)(W-CHCCI^) obtained in Example 2 was weighed 0.009g ( 0.012 mmol) was placed in 20 mL of sample vial, and 3 mL of CH2C 12 was added to dissolve. 2. Scale 0· 004g (0. 021mmol) of AgBF4 Put 5mL sample v i a 1, add 2mL of CH2C 12, dissolve it, add the catalyst added to step 1· with a pipette and stir for 40 minutes. 3. Weigh 0.005g (0.051mmol) of CuCl into 5mL sample vial, add 1mL of CH2C12, dissolve it, add it to step 2·, stir 1 0 m i η, and then inject into step one to start the reaction. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 11 I. Monomer pretreatment In a 50 mL reaction flask, degas purified to 1 uene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1. The catalyst Pd obtained in Example 3 (PPh3) 2(Br)[ 7?1-C(Me)CCH2] Scale 0·03 7g (0·048mmol) was placed in 20 mL sample vial, and 3 mL of C6H5C1 was added to dissolve. 2·Weighing 0·0 28g (0·081mmol) of AgSbF6 Put 5mL sample v i a 1, add 2 m L of C6 H5 C 1, dissolve it, and add it to the catalyst in step 1 by pipetting. After stirring 3 0 m i η, the reaction was started by injecting into the first step. Third, the product after the reaction is completed, add MeOH to settle, and then filter,
0424-7258TWF;02900035;Ca t hy.p t d 第17頁 1301490 五、發明說明（13) 產物置於烘箱中隔夜烘乾，秤重1. 9 7g。 實施例1 2 一、 單體前處理 在50mL之反應槪中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·將實施例3所得之觸媒Pd(PPh3) 2(Br)[ π1 -C(Me)CCH2]秤0· 0 37g(0· 048mmol)置入2 0mL sample vial，加入 3mL 之 CH2C12，使溶解之。 2·秤 0.016g( 0.082mmol)之 AgBF4 置入 5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1.中之觸媒。攪拌40 min後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾、之，將 產物置於烘箱中隔夜烘乾，秤重1. 2 7 g。 實施例1 3 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·將實施例3所得之觸媒Pd(PPh3) 2(Br)[ T^-CUeWCHJ 秤0· 0 37g( 0. 048mmol)置入20mL sample vial，加入3mL 之C6H5C1，使溶解之。04 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 1 2 I. Pretreatment of monomer In 50 mL of reaction hydrazine, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · The catalyst Pd (PPh3) obtained in Example 3 (Br) [ π1 -C(Me)CCH2] Scale 0·0 37g (0·048mmol) was placed in 20 mL sample vial, and 3 mL of CH2C12 was added to dissolve. 2. Weigh 0.016g (0.082mmol) of AgBF4 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, and add it to the catalyst in step 1. by pipetting. After stirring for 40 min, the reaction was started by injecting into the first step. I. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 1 3 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · The catalyst Pd (PPh3) obtained in Example 3 (Br) [T^-CUeWCHJ scale 0·0 37g (0.048 mmol) was placed in 20 mL sample vial, and 3 mL of C6H5C1 was added to dissolve.
0424-7258TWF;02900035;Ca t hy.p t d 第18頁 1301490 五、發明說明（14) 2.秤0· 028g(0· 081mmol)之AgSbF6 置入5mL sample v i a 1，加入2 m L之C6 H5 C 1，使溶解之，用滴管吸取加入步驟 1.中之觸媒中。攪拌3 0 m i η後，注入步驟一中，開始反 應。 三、待反應完後之產物，加入Me0Η使沈降，再過渡之，將 產物置於烘箱中隔夜烘乾，秤重1. 69g。 實施例1 4 一、 單體前處理 在5 0mL之反應瓶中，degas純化之to 1 uene 20mL和 norbornene(85 wt%)4mL o 二、 觸媒 1·將實施例3所得之觸媒Pd(PPh3)2(Br)[ 771-C(Me)CCH2]*0.037g(0.048mmol)4A20mLsample vial，加入3mL之CH2C12，使溶解之。 2.秤0.016g( 0.082minol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入Me0Η使沈降，再過遽之，將 產物置於烘箱中隔夜烘乾，秤重2. 56g。 實施例1 5 一、單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和0424-7258TWF; 02900035; Ca t hy.ptd Page 18 1301490 V. Invention description (14) 2. Scale 0·028g (0·081mmol) of AgSbF6 Put 5mL sample via 1 and add 2 m L of C6 H5 C 1. Dissolve and add to the catalyst in step 1. by pipetting. After stirring 3 0 m i η, it is injected into step one to start the reaction. I. The weight of the product was 1. 69g. The product was placed in an oven overnight and weighed 1. 69g. Example 1 4 1. Monomer pretreatment In a 50 mL reaction flask, degas purified to 1 uene 20 mL and norbornene (85 wt%) 4 mL o 2. Catalyst 1· The catalyst Pd obtained in Example 3 ( PPh3) 2 (Br) [ 771-C (Me) CCH 2 ] * 0.037 g (0.048 mmol) 4A 20 mL sample vial, 3 mL of CH 2 C 12 was added to dissolve. 2. Weigh 0.016g (0.082minol) of AgBF4 into 5mL sample vial, add 2mL of CH2C12, dissolve it, and add it to the catalyst in step 1 by pipetting. After stirring 3 0 m i η, the reaction was started by injecting into the first step. I. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 1 5 1. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and
0424-7258TWF;02900035;Ca t hy.p t d 第19頁 1301490 五、發明說明（15) norbornene(85 wt%)4mL 〇 二、 觸媒 1·將實施例 3 之觸媒 Pd(PPh3)2(Br)[ T^-CUeKCHJ 秤 0.037g(0.048mmol)置入2〇mL sample vial ，加入3mL 之 CH2 C 12，使溶解之。 2·秤0· 016g(0· 082mmol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1·中之觸媒，並攪拌30 min。 3·秤0.022g(0· 0 8mmol)之Ni(C0D)2 置入2 0mL sample vial，加入5mL之toluene，使溶解之，再加入步驟2·中。 攪拌5 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重2. 38g。 實施例1 6 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 。 二、 觸媒 1.將實施例3之觸媒？(1(??}13)2(81〇[771-0：(^16)(：(：112]秤 0.037g(0.048mmol)置入2〇mL sample vial，加入3mL 之 CH2 C 12，使溶解之。 2·秤0· 016g(0. 082mmol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟0424-7258TWF; 02900035; Ca t hy.ptd Page 19 1301490 V. Description of the invention (15) norbornene (85 wt%) 4 mL bismuth, catalyst 1. The catalyst Pd(PPh3)2 of Example 3 (Br) [T^-CUeKCHJ scale 0.037g (0.048mmol) was placed in 2〇mL sample vial, and 3mL of CH2 C 12 was added to dissolve. 2·Weighing 0· 016g (0· 082mmol) of AgBF4 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, add the catalyst added to step 1· with a pipette, and stir for 30 minutes. 3. Weigh 0.022g (0·0 8mmol) of Ni(C0D)2 Put 20mL sample vial, add 5mL of toluene, dissolve it, and add it to step 2·. After stirring 5 m i η, it is injected into the first step to start the reaction. I. The weight of the product was 2.38 g. The product was placed in an oven overnight and weighed 2.38 g. Example 1 6 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL. Second, the catalyst 1. Will the catalyst of Example 3? (1(??}13)2(81〇[771-0:(^16)(:(:112) scale 0.037g (0.048mmol) was placed into 2〇mL sample vial, and 3mL of CH2 C 12 was added to make Dissolve. 2·Weighing 0· 016g (0. 082mmol) of AgBF4 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, add step by pipetting
0424-7258TW;02900035;Cathy.ptd 第20頁 1301490 五、發明說明（16) 1·中之觸媒，並攪拌30 min。 3.秤0.009g(0.081mmol)之CuCl 置入5mL sample vial，加入2mL之CH2C12，再加入步驟2·中。攪拌l〇 min 後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重2. 1 9g。 實施例1 7 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL ° 二、 觸媒 1·將實施例3所得之觸媒Pd(PPh3)2(Br)[ π1-C(Me)CCH2]秤0.009g(0.012mmol)置入20mLsample vial， 加入3mL之C6H5C1，使溶解之。 2·秤 0.0 0 7g(0.02mmol)之 AgSbF6 置入 5mL sample vial，加入2mL之C6H5C1，使溶解之，用滴管吸取加入步驟 1.中之觸媒，並攪拌40 min。 3·秤0.005g(0.051mmol)之CuCl 置入5mL sample vial，加入2mL之C6H5C1，使溶解之，再加入步驟2·中。攪 拌隔夜後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 22g。0424-7258TW; 02900035; Cathy.ptd Page 20 1301490 V. Inventive Note (16) 1· The catalyst is stirred for 30 min. 3. Weighing 0.009 g (0.081 mmol) of CuCl into 5 mL sample vial, adding 2 mL of CH2C12, and adding to step 2·. After stirring for 10 min, the reaction was started by injecting into step one. I. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 1 7 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL ° 2. Catalyst 1· The catalyst Pd (PPh3) obtained in Example 3 (Br) [π1-C(Me)CCH2] scale 0.0099 g (0.012 mmol) was placed in 20 mL sample vial, and 3 mL of C6H5C1 was added to dissolve. 2·Weighing 0.0 0 7g (0.02mmol) of AgSbF6 Put 5mL sample vial, add 2mL of C6H5C1, dissolve it, add it to the catalyst in step 1. with a pipette and stir for 40 minutes. 3. Weigh 0.005 g (0.051 mmol) of CuCl into 5 mL sample vial, add 2 mL of C6H5C1, dissolve it, and add to step 2. After stirring overnight, the mixture was injected into the first step to start the reaction. And the weight was 1.22g. The product was placed in an oven and dried overnight. The weight was 1.22g.
0424-7258TWF;02900035;Ca t hy.p t d 第21頁 1301490 五、發明說明（17) 實施例1 8 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL o 二、 觸媒 1·觸媒Pd(PPh3)4 秤0· 044g( 0. 0 38mmol)置入20mL sample vial，加入3mL之Et20，使溶解之。 2. 秤0.015g(0.126mmol)之C3H3Br 置入5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1. 5 hr。 3. 靜置lmin後，取下層之固體，加入3mL CH2C12。 4·秤0.016g( 0.082mmol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12使溶解。 5.將步驟4.用滴管吸取加入步驟3.中之觸媒。攪拌1 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱隔夜烘乾，秤重2. 1 7 g。 實施例1 9 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒0424-7258TWF; 02900035; Ca t hy.ptd Page 21 1301490 V. INSTRUCTIONS (17) EXAMPLE 1 8 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4mL o 2. Catalyst 1·catalyst Pd(PPh3)4 Scale 0·044g (0.03 mmol) was placed in 20 mL sample vial, and 3 mL of Et20 was added to dissolve. 2 hr. The mixture was stirred and added to the solution of the catalyst in step 1······················ 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of CH2C12. 4. Set 0.016 g (0.082 mmol) of AgBF4 into 5 mL sample vial and add 2 mL of CH2C12 to dissolve. 5. Add step 4. Pipette to the catalyst in step 3. After stirring 1 m i η, it is injected into the first step to start the reaction. I. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Example 1 9 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL 〇 2. Catalyst
1.觸媒Pd(PPh3)4 秤0· 〇llg(〇· 0095mmol)置入20mL1. Catalyst Pd(PPh3)4 Scale 0· 〇llg (〇·0095mmol) placed in 20mL
0424-7258TWF;02900035;Ca t hy.p t d 第22頁 1301490 五、發明說明（18) sample vial，加入3mL之Et20，使溶解之。 2.秤 0.0 04g( 0.0 33mmol)之 C3H3Br 置入 5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1. 5 hr。 3·靜置lmin後，取下層之固體，加入3mL CH2C12。 4. 秤0.004g((K021mmol)之AgBF4 置入5mL sample vial，加入2mL之0112012使溶解。 5. 將步驟4.用滴管吸取加入步驟3.中之觸媒，攪拌1 hr ° 6. 秤0.005g(0.051mmol)之CuCl 置入5mL sample vial，加入2mL之CH2C12，使溶解之，再加入步驟5.中。攪 拌1 0 m i η後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱隔夜烘乾，秤重1. 7 4 g。 實施例2 0 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL ° 二、 觸媒 1.觸媒？(1(卩？]13)4秤0.0112(0.0095111111〇1)置入201111 sample vial，力口入3mL 之tο 1 uene，使溶解之 ° 2·秤 0.004g( 0.033mmol)之 C3H3Br 置入 5mL sample vial，加入2mL之toluene，用滴管吸取加入步驟ι·中之觸0424-7258TWF; 02900035; Ca t hy.p t d Page 22 1301490 V. Inventive Note (18) Sample vial, add 3 mL of Et20 to dissolve. 2 hr. The mixture was added to the solution of the catalyst in the step 1·, and the mixture was stirred for 1.5 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of CH2C12. 4. Weigh 0.004g ((K021mmol) of AgBF4 into 5mL sample vial, add 2mL of 0112012 to dissolve. 5. Add step 4. Pipette to the catalyst in step 3. Stir 1 hr ° 6. Scale 0.005g (0.051mmol) of CuCl was placed in 5mL sample vial, 2mL of CH2C12 was added to dissolve, and then added to step 5. After stirring 10 μm, it was injected into step one to start the reaction. After the product, MeOH was added to make a precipitate, and the mixture was filtered, and the product was placed in an oven overnight, and weighed 1. 7 4 g. Example 2 0 1. Monomer pretreatment In a 50 mL reaction flask, degas was purified. Toluene 20mL and norbornene (85 wt%) 4mL ° Second, the catalyst 1. Catalyst? (1 (卩?) 13) 4 scale 0.0112 (0.0095111111〇1) placed in 201111 sample vial, force into 3mL of tο 1 uene Put the dissolved C3H3Br into 0.005g (0.033mmol) of C3H3Br into 5mL sample vial, add 2mL of toluene, and add to the touch of step ι· with a pipette
0424-7258TWF;02900035;Ca t hy.p t d 第23頁 1301490 五、發明說明（19) 媒，並攪拌1. 5 hr。 3·秤0· 0 04g(0· 021mmol )之AgBF4 置入5mL sample vial，加入5mL之(：112(：12使溶解。 4 ·將步驟3 ·用滴管吸取加入步驟2 ·中之觸媒。授拌i hr後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱隔夜烘乾，秤重h 3 2 g。 實施例2 1 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒04 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. 3·Weighing 0·0 04g (0· 021mmol) of AgBF4 Put 5mL sample vial, add 5mL (: 112 (: 12 to dissolve. 4 · Step 3 • Pipette with pipette added to step 2 · Catalyst After mixing i hr, the reaction was started by injecting into step 1. 3. After the reaction was completed, the product was precipitated by adding MeOH, and then filtered, and the product was placed in an oven overnight to be weighed and weighed by h 3 2 g. Example 2 1 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst
1·觸媒Pd(PPh3)4 秤0· 011g(0· 0 0 95mmol)置入20mL 4 sample vial，加入3mL之Et20，使溶解之。 2. 秤0.0 04g( 0.033mmol)之C3H3Br 置入5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1. 5 hr。 3. 靜置lmin後’取下層之固體’加入3mL CH2C12。 4·秤0· 004g(0· 021mmol)之AgBF4 置入5mL sample vial，加入2mL之(：112(：12使溶解。 5. 將步驟4.用滴管吸取加入步驟3·中之觸媒，攪拌1 hr 〇 6. 秤0· 012g( 0. 0 23mmol)之B(C6F5)3 置入5mL sample1. Catalyst Pd (PPh3) 4 Scale 0· 011g (0·0 0 95 mmol) was placed in 20 mL of 4 sample vial, and 3 mL of Et20 was added to dissolve. 2 hr. The mixture was added to the solution of the catalyst in step 1·, and stirred for 1.5 hr. 3. After standing for 1 min, 'Retain the lower layer' and add 3 mL of CH2C12. 4·Weighing 0· 004g (0· 021mmol) of AgBF4 Put 5mL sample vial, add 2mL (: 112 (: 12 to dissolve. 5. Step 4. Use pipette to add to the catalyst in step 3. Stir 1 hr 〇 6. Scale 0· 012g (0. 0 23mmol) of B(C6F5)3 Place 5mL sample
0424-7258TWF;02900035;Ca t hy.p t d 第24頁 1301490 五、發明說明（20) vial，加入lmL之CH2C12，使溶解之，再加入步驟5·中。攪 拌1 0 m i η後，注入步驟一中，開始反應。。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱隔夜烘乾，秤重1. 42g。 實施例2 2 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·觸媒Pd(PPh3)4 秤0· 0 22 g(0· 019mmol)置入2 0mL sample vial，加入3mL之Et20，使溶解之。 2. 秤 0.0 08g( 0.066mmol)之 C3H3Br 置入 5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1 hr。 3. 靜置lmin後，取下層之固體，加入3mL C6H5C1。 4. 秤(K014g(0.041mmol)之 AgSbF6 置入 5mL sample vial，加入2mL之C6H5C1使溶解。 5 ·將步驟4 ·用滴管吸取加入步驟3 ·中之觸媒。授摔3 hr後，注入步驟一中，開始反應。。 三、 待反應完後之產物，加入MeOH使沈降’再過濾之，將 產物置於烘箱隔夜烘乾，秤重1 · 2 8 g ° 實施例2 30424-7258TWF; 02900035; Ca t hy.p t d Page 24 1301490 V. Inventive Note (20) vial, add 1 mL of CH2C12, dissolve it, and add it to step 5. After stirring 10 m i η, the reaction was started by injecting into the first step. . The product was weighed overnight. The product was placed in an oven overnight and weighed 1.42 g. Example 2 2 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1·catalyst Pd (PPh3) 4 scale 0· 0 22 g (0· 019 mmol) was placed in 20 mL of sample vial, and 3 mL of Et20 was added to dissolve. 2. Scale 0.0 08g (0.066mmol) of C3H3Br into 5mL sample vial, add 2mL of Et20, pipet the catalyst added to step 1· with a pipette and stir for 1 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of C6H5C1. 4. Scale (K014g (0.041mmol) AgSbF6 into 5mL sample vial, add 2mL of C6H5C1 to dissolve. 5 · Step 4 · Pipette with pipette to add the catalyst in step 3 · After 3 hr, inject In the first step, the reaction is started.. 3. After the reaction, the product is added, MeOH is added to make the precipitate, and the product is again filtered. The product is placed in an oven overnight to be weighed and weighed 1 · 2 8 g °. Example 2 3
0424-7258TWF;02900035;Cathy.ptd 第25頁 1301490 五、發明說明（21) 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt% )4mL o 二、 觸媒 1.觸媒Pd(PPh3)4 秤0. 011g( 0. 0 0 9 5mmol)置入2 0mL sample vial，加入3mL之Et20，使溶解之。 2·秤0· 002g(0. 022mmol)之C4H7C1 置入5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1· 5 hr。 3·靜置lmin後，取下層之固體，加入3mL CH2C12。 4·科0· 004g(0. 021mmol)之AgBF4 置入5mL sample vial，加入2mL之(]112(^12使溶解。 5.將步驟4.用滴管吸取加入步驟3.中之觸媒。攪拌1 hr後，注入步驟一中，開始反應。。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱隔夜烘乾，秤重0 . 3 7 g。 實施例24 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·實施例 4 所得之觸媒[Pd(PPh3)2( 773-CH2CCMe)]BF4秤 0.024g(0.031mmol)置入20mL sample vial，加入5mL 之0424-7258TWF; 02900035; Cathy.ptd Page 25 1301490 V. INSTRUCTIONS (21) I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL o Medium 1. Catalyst Pd(PPh3)4 Scale 0. 011g (0.09 9 5mmol) was placed in 20 mL sample vial, and 3 mL of Et20 was added to dissolve. 2. Scale 0·002g (0. 022mmol) of C4H7C1 Put 5mL sample vial, add 2mL of Et20, add the catalyst added to step 1· with a pipette, and stir for 1.5 hours. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of CH2C12. 4·科0· 004g (0. 021mmol) of AgBF4 Put 5mL sample vial, add 2mL of () 112 (^12 to dissolve. 5. Step 4. Pipette the pipette into the catalyst in step 3. After stirring for 1 hr, the reaction was started by injecting into the first step. 3. After the reaction was completed, the product was precipitated by adding MeOH, and then filtered, and the product was placed in an oven overnight to be weighed and weighed 0.37 g. Example 24 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · Catalyst obtained in Example 4 [Pd(PPh3) 2 ( 773 -CH2CCMe)] BF4 scale 0.024g (0.031mmol) was placed in 20mL sample vial, added 5mL
0424-7258TWF;0290003 5;Ca t hy.p t d 第26頁 1301490 五、發明說明（22) CH2.C 12，使溶解之，然後注入步驟一中，開始反應。 將 三、待反應完後之產物，加入MeOH使沈降，再過濾之 產物置於烘箱中隔夜烘乾，秤重〇 . 2 4 g。 實施例2 5 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL ° 二、 觸媒 1·實施例 4 所得之觸媒[Pd(PPh3)2( ?73-CH2CCMe)]BF4* 0.038g( 0.049mmol)置入 20mL sample vial，加入 3mL 之 CH2C 12，使溶解之。 2·秤0· 022g(0· 08mmol)之Ni(C0D)2 置入5mL sample vial，加入2mL之toluene，使溶解之，用滴管吸取加入步 驟1 ·中之觸媒。攪拌5 m i η後，注入步驟一中，開始反 應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重0 . 2 1 g。 i 實施例2 6 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL ° 二、 觸媒0424-7258TWF;0290003 5;Ca t hy.p t d Page 26 1301490 V. INSTRUCTION DESCRIPTION (22) CH2.C 12, dissolved, and then injected into step one to start the reaction. 3. After the reaction, the product after completion of the reaction was added to MeOH to make a sediment, and the filtered product was placed in an oven and dried overnight, weighing 〇 2 4 g. Example 2 5 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL ° 2. Catalyst 1 · Catalyst obtained in Example 4 [Pd(PPh3) 2 (?73-CH2CCMe)] BF4* 0.038 g (0.049 mmol) was placed in 20 mL of sample vial, and 3 mL of CH2C 12 was added to dissolve. 2. Weigh 0· 022g (0·08mmol) of Ni(C0D)2 Put 5mL sample vial, add 2mL of toluene, dissolve it, and add it to the catalyst in step 1 by pipette. After stirring 5 m i η, inject into step one to start the reaction. 3. After the reaction, the product was reacted, MeOH was added to precipitate, and the mixture was filtered. The product was placed in an oven and dried overnight, and weighed 0.21 g. i Example 2 6 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL ° II, catalyst
0424-72 58TWF;02900035;Ca t hy.p t d 第27頁 1301490 五、發明說明（23) 1·實施例 4 所得之觸媒[Pd(PPh3)2( 7/3-CH2CCMe)]BF4 秤 0.038g(0.049mmol)置入20mL sample vial ，加入3mL 之 CH2C12，使溶解之。 2·秤0.008g(0.081mmol)之CuCl 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌5 m i η後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 72g。0424-72 58TWF; 02900035; Ca t hy.ptd Page 27 1301490 V. Inventive Note (23) 1. Example 4 Catalyst [Pd(PPh3)2(7/3-CH2CCMe)]BF4 Scale 0.038g (0.049 mmol) was placed in 20 mL of sample vial, and 3 mL of CH2C12 was added to dissolve. 2. Weighing 0.008 g (0.081 mmol) of CuCl into 5 mL sample vial, adding 2 mL of CH2C12, dissolving, and pipetting into the catalyst in step 1. After stirring 5 m i η, it is injected into the first step to start the reaction. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。.
實施例2 7 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·實施例 4 所得之觸媒[Pd(PPh3)2( 7?3-CH2CCMe)]BF4-0.0 0 6g( 0.0 0 78mmol)置入 20mL sample vial，加入 3mL 之 C6H5C1，使溶解之。 2.秤0.0 0 7g(0.02mmol)之AgSbF6 置入5mL sample v i a 1，加入2 m L之C6 H5 C 1，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。授拌3 0 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重0 . 4 1 g。 實施例2 8Example 2 7 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · Catalyst obtained in Example 4 [Pd(PPh3)2 (7?3-CH2CCMe)] BF4-0.0 0 6g (0.00 78 mmol) was placed in 20 mL of sample vial, and 3 mL of C6H5C1 was added to dissolve. 2. Weigh 0.0 0 7g (0.02mmol) of AgSbF6 into 5mL sample v i a 1, add 2 m L of C6 H5 C 1, dissolve it, and add to the catalyst in step 1 by pipetting. After mixing 3 0 m i η, the reaction is started by injecting into the first step. 3. After the reaction was completed, MeOH was added to precipitate, and the mixture was filtered, and the product was placed in an oven and dried overnight to weigh 0.41 g. Example 2 8
0424-7258TWF;02900035;Ca t hy.p t d 第28頁 1301490 五、發明說明（24) 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1.實施例 4 所得之觸媒[Pd(PPh3)2( ?73-CH2CCMe)]BF4 秤 0.006g(0.0078mmol)置入20mL sample vial，加入3mL 之 C6 H5 C 1，使溶解之。 2·秤0· 0 0 5g(0· 026mmol)之AgBF4 置入5mL sample0424-7258TWF; 02900035; Ca t hy.ptd Page 28 1301490 V. INSTRUCTIONS (24) I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL Catalyst 1. Example 4 The obtained catalyst [Pd(PPh3)2(?73-CH2CCMe)]BF4 scale 0.006g (0.0078mmol) was placed in 20mL sample vial, and 3mL of C6 H5 C1 was added to dissolve . 2·Scale 0· 0 0 5g (0· 026mmol) of AgBF4 placed in 5mL sample
vial，加入2mL之C6H5C1，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反 應。0 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重〇. 83g。 實施例2 9 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1.實施例 5 所得之觸媒[Pd(PPh3)2( 773-CH2C(CMe) (NHCH2-)]2(BF4)2 种0· 022g(0· 014mmol)置入20mL sample vial，加入3mL之CH2C12，使溶解之。 2·秤 0.0 0 7g( 0.0 0 2mmol)之 AgSbF6 置入 5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟Vial, add 2mL of C6H5C1, dissolve it, and add it to the catalyst in step 1 by pipetting. After stirring 3 0 m i η, it is injected into step one to start the reaction. 0. After the reaction, the product was precipitated by adding MeOH, and then filtered, and the product was placed in an oven and dried overnight, weighing 83 83 g. Example 2 9 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1. Catalyst obtained in Example 5 [Pd(PPh3)2 (773-CH2C(CMe)(NHCH2-)]2(BF4) 2 kinds of 0·022g (0·014mmol) were placed in 20mL sample vial, and 3mL of CH2C12 was added to dissolve it. 2·Weighing 0.0 0 7g ( 0.0 0 2mmol) of AgSbF6 was placed in 5mL sample vial, 2mL of CH2C12 was added to dissolve, and the step of adding by pipette was added.
0424-7258TWF;02900035;Ca t hy.p t d 第29頁 1301490 五、發明說明（25) 1 ·中之觸媒。攪拌1 h r後，注入步驟一中，加熱至5 〇 °C， 開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1· 52g。 實施例3 0 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和0424-7258TWF; 02900035; Ca t hy.p t d Page 29 1301490 V. Description of invention (25) 1 · Catalyst in medium. After stirring for 1 h, the mixture was injected into the first step and heated to 5 〇 ° C to start the reaction. 3. After the reaction, the product was precipitated by adding MeOH, and then filtered, and the product was placed in an oven and dried overnight to weigh 1.52 g. Example 3 0. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and
norbornene(85 wt%)4mL 〇 二、 觸媒 1·實施例 5 所得之觸媒[Pd(PPh3)2( τ?3-CH2C(CMe) (NHCH2-) ]2(BF4)2 秤0· 0 2 2g(0· 014mmol)置入20mL sample vial，加入3mL之C6H5C1，使溶解之。 2·秤0.0 07g( 0.002mmol)之AgSbF6 置入5mL sample vial，加入2mL之C6H5C1，使溶解之，用滴管吸取加入步驟 1.中之觸媒。攪拌1 hr後，注入步驟一中，加熱至50 °C， 開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾、之，將 產物置於烘箱中隔夜烘乾，秤重1. 86g。 實施例3 1 一、單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL oNorbornene (85 wt%) 4 mL 〇2, Catalyst 1·Example 5 The resulting catalyst [Pd(PPh3)2( τ?3-CH2C(CMe) (NHCH2-) ]2(BF4)2 Scale 0· 0 2 2g (0·014mmol) was placed in 20mL sample vial, and 3mL of C6H5C1 was added to dissolve it. 2·Weigh 0.0 07g (0.002mmol) of AgSbF6 into 5mL sample vial, add 2mL of C6H5C1, dissolve it, use drops The pipe is added to the catalyst in the step 1. After stirring for 1 hr, it is injected into the first step, and heated to 50 ° C to start the reaction. 3. After the reaction, the product is added, MeOH is added to precipitate, and then filtered, The product was oven-dried overnight and weighed 1.86 g. Example 3 1 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL o
0424-7258TWF;02900035;Ca t hy.p t d 第30頁 1301490 五、發明說明（26) 二、 觸媒 1·實施例 5 所得之觸媒[Pd(PPh3)2( ??3-CH2C(CMe) (NHCH2-)]2(BF4)2 秤0· 〇22g(0· 〇14mmol)置入20mL sample v i a 1，加入3 m L之C6 H5 C 1，使溶解之。 2·秤 0.0 0 5g(0.02mmol)之 CuCl 置入 5mL sample vial，加入2mL之C6H5C1，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌1 hr後，注入步驟一中，開始反應。 三、 反應 lhr 後，秤0.012g( 0.0 23mmol)之 B(C6F5)3 置入 5mL sample vial，加入2mL之CH2C12，使溶解之，用針筒吸 取，並注入步驟二中，繼續反應。 四、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重〇 . 3 1 g。 實施例3 2 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·實施例 5 所得之觸媒[Pd(PPh3)2( 773-CH2C(CMe) (NHCH2-)]2(BF4)2 秤0· 022g(0. 014mmol)置入20mL sample vial，加入3mL之CH2C12，使溶解之。 2·秤0· 012g(0· 023mmol)之B(C6F5)3 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌1 h r後，注入步驟一中，開始反應。0424-7258TWF; 02900035; Ca t hy.ptd Page 30 1301490 V. Description of invention (26) II. Catalyst 1·Example 5 Catalyst obtained [Pd(PPh3)2(??3-CH2C(CMe) (NHCH2-)]2(BF4)2 Scale 0· 〇22g (0·〇14mmol) was placed in 20mL sample via 1, and 3 m L of C6 H5 C 1 was added to dissolve it. 2·Weighing 0.0 0 5g (0.02 Add 2.5 mL of CuCl into 5 mL sample vial, add 2 mL of C6H5C1, dissolve it, and add to the catalyst in step 1 by pipetting. After stirring for 1 hr, inject into step one to start the reaction. , weighing 0.012g (0.0 23mmol) of B(C6F5)3 into 5mL sample vial, adding 2mL of CH2C12, dissolving it, sucking it with a syringe, and injecting into step 2, continue the reaction. 4. After the reaction is completed The product was added to MeOH to make a precipitate, and then filtered. The product was placed in an oven and dried overnight, weighing 〇 3 3 g. Example 3 2 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · Catalyst obtained in Example 5 [Pd(PPh3)2( 773-CH2C(CMe) (NHCH2-)] 2(BF4)2 Scale 0· 022g (0. 014mmol) set 20mL sample vial, add 3mL of CH2C12 to dissolve. 2· Scale 0· 012g (0·023mmol) of B(C6F5)3 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, add it with pipette Step 1 · Catalyst in the medium. After stirring for 1 hr, inject into the first step and start the reaction.
0424-7258TWF;02900035;Ca t hy.p t d 第31頁 1301490 五、發明說明（27) 三、待反應完後之產物，加入Me〇H使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重〇 · 2 6g。 實施例3 3 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt°/〇)4mL 。 二、 觸媒0424-7258TWF; 02900035; Ca t hy.ptd Page 31 1301490 V. Description of invention (27) 3. After the reaction, the product is added, Me〇H is added to make the sediment, and then filtered, the product is placed in an oven and baked overnight. Dry, weighing 〇 · 2 6g. Example 3 3 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt ° / 〇) 4 mL. Second, the catalyst
1·實施例 6 所得之觸媒[Pd(PPh3)2( ?73-CH2C(NEt2) (CMe) ]SbF6 秤〇· 〇14g(0· 〇14mmol )置入2 0mL sample vial，加入5mL之CH2C12，使溶解之。接著，注入步驟一 中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重〇. 〇 1 8g。 實施例34 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 。 二、 觸媒 1·實施例 6 所得之觸媒[Pd(PPh3)2( 7y3-CH2C(NEt2) (CMe)]SbF6秤0·028g(0·028mmol)置入20InLsamρle vial，加入3mL之CH2C12，使溶解之。 2·秤 0.010g(0.01mm〇l)之 CuCl 置入 5mL sample1. Example 6 The obtained catalyst [Pd(PPh3)2(?73-CH2C(NEt2)(CMe)]SbF6 scale 〇14g (0·〇14mmol) was placed in 20 mL sample vial, and 5 mL of CH2C12 was added. Then, it is dissolved. Then, the reaction is started by injecting into the first step. 3. After the reaction, the product is added, MeOH is added to precipitate, and then filtered, and the product is placed in an oven to be dried overnight, and weighed. 〇1 8g Example 34 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL. 2. Catalyst 1·Example 6 Catalyst obtained [Pd(PPh3)2 (7y3-CH2C(NEt2) (CMe)] SbF6 scale 0·028g (0·028mmol) was placed in 20InLsamρle vial, and 3mL of CH2C12 was added to dissolve it. 2. Scale 0.010g (0.01mm〇l) of CuCl was placed 5mL sample
0424-7258TWF;02900035;Ca t hy.p t d 第32頁 1301490 五、發明說明（28) v i a 1，加入2 m L之C H2 C 12，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重〇 · 2 1 g。 實施例3 5 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·實施例 6 所得之觸媒[Pd(PPh3)2( 7?3-CH2C(NEt2) (0乂6)]8乜卩6秤0.0148(0.014111111〇1)置入20mL sample vial，加入3mL之CH2C12，使溶解之。 2·秤0· 007g(0. 02mmol)之AgSbF6 置入5mL sample v i a 1，加入2 m L之C H2 C 12，使溶解之，用滴管吸取加入步驟 1.中之觸媒。攪拌1 hr後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 76g。 實施例3 6 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒0424-7258TWF; 02900035; Ca t hy.ptd Page 32 1301490 V. Description of invention (28) via 1, add 2 m L of C H2 C 12, dissolve it, add it with a pipette and add it to step 1 Media. After stirring 3 0 m i η, the reaction was started by injecting into the first step. 3. After the reaction, the product was precipitated by adding MeOH, and then filtered, and the product was placed in an oven and dried overnight to weigh 2 2 1 g. Example 3 5 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1 · Catalyst obtained in Example 6 [Pd(PPh3)2 (7?3-CH2C(NEt2)(0乂6)]8乜卩6 scale 0.0148 (0.014111111〇1) was placed in 20mL sample vial, and 3mL of CH2C12 was added to dissolve it. 2·Scale 0· 007g (0. 02mmol) of AgSbF6 was placed in 5mL sample via 1, 2 m L of CH 2 C 12 was added, dissolved, and pipetted into the catalyst in step 1. After stirring for 1 hr, inject into step one and start the reaction. After the reaction, the product was reacted, MeOH was added to precipitate, and the mixture was filtered. The product was placed in an oven overnight and weighed 1.76 g. Example 3 6 I. Monomer pretreatment in a 50 mL reaction bottle , degas purified toluene 20mL and norbornene (85 wt%) 4mL bismuth, catalyst
0424-7258TWF;02900035;Ca t hy.p t d 第33頁 1301490 五、發明說明（29) 1·觸媒Pd(PPh3)4 秤0· 011g(0· 0 0 9 5mmol)置入20mL sample vial，加入3mL 之CH2C12，使溶解之。 2.秤0· 005g(0· 026mmol)之AgBF4 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1·中之觸媒。攪拌30 min後，注入步驟一中，開始反應。 三、待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重0. 49g。0424-7258TWF; 02900035; Ca t hy.ptd Page 33 1301490 V. Description of invention (29) 1. Catalyst Pd(PPh3)4 Scale 0· 011g (0·0 0 9 5mmol) placed in 20mL sample vial, added 3mL of CH2C12 is dissolved. 2. Scale 0·005g (0·026mmol) of AgBF4 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, and add it to the catalyst in step 1 by pipetting. After stirring for 30 min, the reaction was started by injecting into the first step. And the weight of the product was weighed at 0. 49g. The product was placed in an oven and dried overnight.
實施例37 一、 單體前處理 在5OmL之反應瓶中，degas純化之tο 1 uene 2OmL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1.觸媒卩(1(??113)4秤0.0112( 0.0 0 9 5111111〇1)置入2 011^ sample vial，加入3mL 之C6H5C1，使溶解之。 2·秤0.0 0 5g( 0.026mmol)之AgBF4 置入5mL sample vial，加入2mL之C6H5C1，使溶解之，用滴管吸取加入步驟 1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 1 2g。 實施例3 8 一、單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和Example 37 I. Monomer pretreatment In a 50 mL reaction flask, degas purified tο 1 uene 2OmL and norbornene (85 wt%) 4 mL 〇2, catalyst 1. Catalyst 卩 (1 (?? 113) 4 scale 0.0112 ( 0.0 0 9 5111111〇1) was placed in 2 011^ sample vial, and 3 mL of C6H5C1 was added to dissolve it. 2·Weighing 0.0 0 5g (0.026 mmol) of AgBF4 was placed in 5 mL sample vial, and 2 mL of C6H5C1 was added to make After dissolving, use a pipette to aspirate the catalyst added in step 1. After stirring 3 0 mi η, inject into step one to start the reaction. 3. After the reaction, the product is added, MeOH is added to precipitate, and then filtered, The product was oven-dried overnight and weighed 1.12 g. Example 3 8 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and
0424-7258TWF;02900035;Ca t hy.p t d 第34頁 1301490 五、發明說明（30) norbornene(85 wt% )4mL o 二、 觸媒 1·觸媒Pd(PPh3)4 秤0· 011g( 0. 0 0 9 5mmol)置入20mL sample vial，加入3mL 之toluene，使溶解之。 2·秤0.005g(0.026mmol)之AgBF4 置入5mL sample vial，加入2mL之toluene，使溶解之，用滴管吸取加入步 驟1 ·中之觸媒。攪拌3 0 m i η後，注入步驟一中，開始反 應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾、之，將 產物置於烘箱中隔夜烘乾，秤重0. 18g。 實施例3 9 一、 單體前處理 在50mL之反應瓶中，degas純化之toluene 20mL和 norbornene(85 wt%)4mL 〇 二、 觸媒 1·觸媒Pd(PPh3)4 秤0· 011g(0· 0 095mmol)置入20mL sample vial，加入 3mL 之 CH2C12，使溶解之。 2·秤0· 007g(0. 02mmol)之AgSbF6 置入5mL sample vial，加入2mL之CH2C12，使溶解之，用滴管吸取加入步驟 1·中之觸媒。攪拌3〇 min後，注入步驟一中，加熱至60 °C，開始反應。 三、 待反應完後之產物，加入MeOH使沈降，再過濾之，將 產物置於烘箱中隔夜烘乾，秤重1. 58g。0424-7258TWF; 02900035; Ca t hy.ptd Page 34 1301490 V. Description of invention (30) norbornene (85 wt%) 4mL o 2. Catalyst 1 · Catalyst Pd (PPh3) 4 Scale 0 · 011g ( 0. 0 0 9 5 mmol) Place 20 mL sample vial and add 3 mL of toluene to dissolve. 2. Weigh 0.005g (0.026mmol) of AgBF4 into 5mL sample vial, add 2mL of toluene, dissolve it, and add to the catalyst in step 1 by pipetting. After stirring 3 0 m i η, it is injected into step one to start the reaction. I. 18g. The weight of the product was weighed in an oven. Example 3 9 I. Monomer pretreatment In a 50 mL reaction flask, degas purified toluene 20 mL and norbornene (85 wt%) 4 mL bismuth, catalyst 1·catalyst Pd (PPh3) 4 scale 0·011g (0 · 0 095 mmol) Place 20 mL sample vial and add 3 mL of CH2C12 to dissolve. 2·Weighing 0·007g (0. 02mmol) of AgSbF6 Put 5mL sample vial, add 2mL of CH2C12, dissolve it, and add it to the catalyst in step 1 by pipetting. After stirring for 3 Torr, the mixture was injected into the first step, heated to 60 ° C, and the reaction was started. And the weight was 1.58g. The product was placed in an oven overnight and weighed 1.58g.
0424-72 58TWF;0290003 5;Ca t hy.p t d 第35頁 1301490 五、發明說明（31) 冰片稀之共聚合 實施例40 : NB與MA共聚操作步驟 一、 單體前處理 在50mL之反應瓶中，degas純化後之norbornene(85 wt % )mL 與MA 4mL 〇 二、 觸媒 1·實施例1 觸媒秤0· 01 lg(〇. 〇〇95minol)置入20mL Sample vial，力口入3mL之Et20，使溶解之。 2·秤0· 0 04g( 0. 033mmol)之C3H3Br 置入5mL Sample vial，加入2mL之Et20，用滴管吸取加入步驟1.中之觸 媒，並攪拌1 hr。 3.靜置lmin後，取得下層固體，加入3mL C6H5C1。 4·秤0· 007g(0· 02mmol)之AgSbF6 置入5mL Sample v i a 1，加入2 m L之C6 H5 C 1使溶解。 5.將步驟4.用滴管吸取加入步驟3.中之觸媒。攪拌30 m i η後，注入步驟一中，加熱至5 0 °C開始反應。 三、 待反應1 h r後，將產物加入M e Ο Η使沈降，再過濾、之， 產物置於烘箱烘乾overnight，秤重0.421 g。 實施例41 :NB與BMA共聚操作步驟 一、單體前處理 在50mL之反應瓶中，degas純化後之norbornene(85 wt% )lmL 與BMA 4mL 〇0424-72 58TWF; 0290003 5; Ca t hy.ptd Page 35 1301490 V. Description of the invention (31) Borneol dilute copolymerization Example 40: Copolymerization of NB and MA Procedure 1. Monomer pretreatment in 50 mL reaction flask In the degas purified norbornene (85 wt%) mL and MA 4mL 〇2, the catalyst 1 · Example 1 catalyst scale 0 · 01 lg (〇. 〇〇 95minol) placed 20mL Sample vial, force into the 3mL Et20, so that it dissolves. 2·Weighing 0·0 04g (0. 033mmol) of C3H3Br was placed in 5 mL of Sample vial, 2 mL of Et20 was added, and the catalyst added to the step 1. was pipetted and stirred for 1 hr. 3. After standing for 1 min, the lower solid was taken and 3 mL of C6H5C1 was added. 4·Weighing 0·007g (0·02mmol) of AgSbF6 Put 5mL Sample v i a 1 and add 2 m L of C6 H5 C 1 to dissolve. 5. Add step 4. Pipette to the catalyst in step 3. After stirring 30 m i η, the mixture was injected into the first step, and heated to 50 ° C to start the reaction. 3. After 1 h of reaction, the product was added to Me Ο Η to make a settling, and then filtered, and the product was placed in an oven to dry overnight, weighing 0.421 g. Example 41: Copolymerization of NB and BMA Procedure 1. Monomer pretreatment In a 50 mL reaction flask, deborne purified norbornene (85 wt%) lmL and BMA 4 mL 〇
0424-7258TWF;02900035;Cathy.ptd 第36頁 1301490 五、發明說明（32) 二、 觸媒 1·實施例1 觸媒秤0· 〇llg(〇. 〇〇95mmol)置入20mL Sample vial，加入3mL之Et20，使溶解之。 2·科0.004g(0.033mmol)之C3H3Br 置入5mL Sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1 hr。 3.將靜置lmin後，取下層之固體，加入3mL C6H5C1。 4·秤0· 007g(0· 02mmol)之AgSbF6 置入5mL Sample vial，加入2mL之C6H5C1使溶解。 5·將步驟4·用滴管吸取加入步驟3·中之觸媒。攪拌30 m i η後，注入步驟一中，加熱至5 0 °C開始反應。 三、 待反應lhr後，將產物加入MeOH使沈降，再過濾之， 產物置於烘箱烘乾overnight，秤重〇.587g。 實施例42 : NB與t-BA共聚操作步驟 一、 單體前處理 、 在50mL之反應瓶中，degas純化後之n〇rbornene(85 wt% )lmL與t-BA 4mL 〇 二、 觸媒 1.實施例1 觸媒秤0· 01 lg(〇. 0 0 95mmol)置入20mL Sample vial，加入3mL之Et20，使溶解之。 2·秤0.004g( 0.033mmol)之C3H3Br 置入5mL Sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1 hr。0424-7258TWF; 02900035; Cathy.ptd Page 36 1301490 V. Invention Description (32) II. Catalyst 1·Example 1 Catalyst scale 0· 〇llg (〇. 〇〇95mmol) placed in 20mL Sample vial, add 3mL of Et20, so that it dissolves. 2. Section 0.004g (0.033mmol) of C3H3Br was placed in 5 mL of Sample vial, 2 mL of Et20 was added, and the catalyst added to Step 1 was pipetted with a pipette and stirred for 1 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of C6H5C1. 4·Weighing 0·007g (0·02mmol) of AgSbF6 Put 5mL Sample vial and add 2mL of C6H5C1 to dissolve. 5. Add the step 4 to the catalyst in step 3 by pipetting. After stirring 30 m i η, the mixture was injected into the first step, and heated to 50 ° C to start the reaction. 3. After 1 hour of reaction, the product was added to MeOH to make a sediment, and then filtered, and the product was placed in an oven to dry overnight, weighing 587 g. Example 42: Copolymerization of NB and t-BA Operation Step 1. Monomer pretreatment, in a 50 mL reaction flask, degas purified n〇rbornene (85 wt%) 1 mL and t-BA 4 mL 〇2, catalyst 1 Example 1 Catalyst scale 0·01 lg (〇. 0 0 95 mmol) was placed in 20 mL of Sample vial, and 3 mL of Et20 was added to dissolve. 2. Weighing 0.004g (0.033mmol) of C3H3Br into 5mL Sample vial, adding 2mL of Et20, pipetting the catalyst added to step 1· with a pipette and stirring for 1 hr.
0424-7258TWF;02900035;Ca t hy.p t d 第37頁 1301490 五、發明說明（33) 3. 靜置lmin後，取下層固體，加入3mL C6H5C1。 4. 秤0· 0 0 7g(0. 02mmol )之AgSbF6 置入5mL Sample v i a 1，加入2 m L之C6 H5 C 1使溶解。 5·將步驟4·用滴管吸取加入步驟3·中之觸媒。攪拌3〇 m i η後，注入步驟一中，加熱至5 0 °C開始反應。 三、待反應2 4 h r後，將產物加入M e 0 Η使沈降，再過濾之， 產物置於烘箱烘乾overnight，秤重0.248g。 實施例43 : NB與t-BA共聚操作步驟 、 單體前處理 在5 OmL之反應瓶中，degas純化後之n orb or nene( 85 wt % )lmL 與t-BA 4mL ° 二、 觸媒 1.實施例1 觸媒秤0· 011g( 0. 0 0 95mmol)置入20mL Sample vial，加入3mL之Et20，使溶解之。 2·秤0.0 04g( 0.033mmol)之C3H3Br 置入5mL Sample vial，加入2mL之Et20，用滴管吸取加入步驟1·中之觸 媒，並攪拌1 hr。 3.靜置lmin後，取下層之固體，加入3mL C6H5C1。 4·科0· 004g(0· 021mmol)之AgBF4 置入5mL Sample v i a 1，加入2 m L之C6 H5 C 1使溶解。 5·將步驟4·用滴管吸取加入步驟3·中之觸媒。攪拌30 m i η後，注入步驟一中，加熱至5 0 °C開始反應。 三、 待反應lhr後，將產物加入MeOH使沈降，再過濾之，0424-7258TWF; 02900035; Ca t hy.p t d Page 37 1301490 V. Inventive Note (33) 3. After standing for 1 min, remove the layer of solid and add 3 mL of C6H5C1. 4. Scale 0·0 0 7g (0. 02mmol) of AgSbF6 Place 5mL Sample v i a 1 and add 2 m L of C6 H5 C 1 to dissolve. 5. Add the step 4 to the catalyst in step 3 by pipetting. After stirring 3 〇 m i η, the mixture was injected into the first step, and heated to 50 ° C to start the reaction. 3. After the reaction is carried out for 24 h, the product is added to the Me 0 Η to make a sediment, and then filtered, and the product is placed in an oven to dry overnight, and the weight is 0.248 g. Example 43: NB and t-BA copolymerization operation step, monomer pretreatment in a 50 mL reaction flask, de orb or nene (85 wt%) lmL and t-BA 4 mL ° after degas purification. Example 1 Catalyst scale 0· 011g (0.00 95 mmol) was placed in 20 mL of Sample vial, and 3 mL of Et20 was added to dissolve. 2. Weigh 0.004g (0.033mmol) of C3H3Br into 5mL Sample vial, add 2mL of Et20, add the catalyst added to step 1· with a pipette and stir for 1 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of C6H5C1. 4·科0· 004g (0· 021mmol) of AgBF4 was placed in 5mL Sample v i a 1, 2 m L of C6 H5 C 1 was added to dissolve. 5. Add the step 4 to the catalyst in step 3 by pipetting. After stirring 30 m i η, the mixture was injected into the first step, and heated to 50 ° C to start the reaction. 3. After reacting for 1 hour, the product is added to MeOH to precipitate, and then filtered.
0424-7258TWF;02900035;Ca t hy.p t d 第38頁 1301490 五、發明說明（34) 產物置於烘箱烘乾overnight，秤重0.434 g。 實施例44 :NB與NB-Si(0Me)3共聚操作步驟 一、 單體前處理 在50mL之反應瓶中，degas純化後之norbornene(85 wt% )lmL 與NB-Si(0Me)3 lmL 〇 二、 觸媒 1·觸媒Pd(PPh3)4 秤0· 011g(0· 〇〇95mmol)置入20mL sample vial，加入3mL之Et20，使溶解之。 2·秤0· 004g(0· 033_〇1)之C3H3Br 置入5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1 ·中之觸 媒，並攪拌1 hr。 3·靜置lmin後，取下層之固體，加入3mL C6H5C1。 4·秤0· 007g(0· 02mmol)之AgSbF6 置入5mL sample vial，加入2mL之C6H5C1使溶解。 5·將步驟4.用滴管吸取加入步驟3.中之觸媒，攪拌30 m i η後，注入步驟一中，開始反應。 三、 待反應2 hr後，將產物加入Me0Η使沈降，再過濾之， 產物置於烘箱隔夜烘乾，秤重2. 8 1 g。 實施例45 一、單體前處理 在5 OmL之反應瓶中，degas純化後之nor born ene( 85 wt% )lmL 與 NB-Si(0Me)3 lmL 〇0424-7258TWF; 02900035; Ca t hy.p t d Page 38 1301490 V. INSTRUCTIONS (34) The product was placed in an oven to dry overnight and weighed 0.434 g. Example 44: Copolymerization of NB and NB-Si(0Me)3 Step 1. Monomer pretreatment In a 50 mL reaction flask, deborne purified norbornene (85 wt%) lmL and NB-Si (0Me) 3 lmL 〇 2. Catalyst 1·catalyst Pd(PPh3)4 Scale 0· 011g (0·〇〇95 mmol) was placed in 20 mL sample vial, and 3 mL of Et20 was added to dissolve. 2· Scale 0· 004g (0· 033_〇1) of C3H3Br Put 5 mL sample vial, add 2 mL of Et20, pipet the catalyst added to step 1 · and stir for 1 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of C6H5C1. 4· Scale 0· 007g (0·02mmol) of AgSbF6 Put 5mL sample vial, add 2mL of C6H5C1 to dissolve. 5. Step 4. Add the catalyst in step 3. by pipetting, stir 30 m i η, and then inject into step one to start the reaction. 8 1 g。 After the reaction was carried out for 2 hr, the product was added to Me0 Η to settle, and then filtered, the product was placed in an oven to dry overnight, weighing 2. 8 1 g. Example 45 I. Monomer pretreatment In a 50 mL reaction flask, deran purified nor born ene (85 wt%) lmL and NB-Si (0Me) 3 lmL 〇
0424-7258TWF;0290003 5;Ca t hy.p t d 第39頁 1301490 五、發明說明（35) 二、觸媒 1·觸媒Pd(PPh3)4 秤〇· 〇llg(〇· 〇〇95mmol)置入20mL sample vial，加入3mL之Et20，使溶解之。 2. 秤0.004g(0.033mmol)之C3H3Br 置入5mL sample vial，加入2mL之Et20，用滴管吸取加入步驟1.中之觸 媒，並攪拌1 hr。 3. 靜置lmin後，取下層之固體，加入3mL C6H5C1。 4·秤0.005g(0. 0 2 6mmol )之AgBF4 置入5mL sample v i a 1，加入2 m L之C6 H5 C 1使溶解。 5 ·將步驟4 ·用滴管吸取加入步驟3 ·中之觸媒。攪拌3 〇 m i η後，注入步驟一中，開始反應。 二、待反應2 hr後，將產物加入Me〇H使沈降，再過濾之， 產物置於烘箱隔夜烘乾，秤重〇 . 2 9 g。 ^ 雖然本發明已以較佳實施例揭露如上，麸1 限定本發明，任何熟習此項 ：二：用以 神和範圍内，當可作更動鱼，Pn 隹个脫離本發明之精 當視後附之申請專利範圍所界定者為準。月之保4乾圍0424-7258TWF;0290003 5;Ca t hy.ptd Page 39 1301490 V. Description of invention (35) 2. Catalyst 1·catalyst Pd(PPh3)4 Scale 〇·〇llg(〇· 〇〇95mmol) placed 20 mL sample vial, 3 mL of Et20 was added to dissolve. 2. A solution of 0.004 g (0.033 mmol) of C3H3Br was placed in 5 mL of sample vial, 2 mL of Et20 was added, and the catalyst added to step 1. was pipetted and stirred for 1 hr. 3. After standing for 1 min, remove the solid from the lower layer and add 3 mL of C6H5C1. 4. Weigh 0.005 g (0.26 mmol) of AgBF4 into 5 mL of sample v i a 1, and add 2 m of C6 H5 C 1 to dissolve. 5 · Step 4 • Pipette with the pipette into the catalyst in step 3. After stirring 3 〇 m i η, the reaction is started by injecting into the first step. 2. After reacting for 2 hr, the product was added to Me〇H to make a sediment, and then filtered, and the product was placed in an oven to be dried overnight, weighing 〇 2 9 g. Although the present invention has been disclosed in the preferred embodiment as above, the bran 1 defines the present invention, and any of the familiar ones are used: two: in the range of God and in the range, when the fish can be changed, Pn is removed from the fine view of the present invention. The scope defined in the patent application is subject to change. Monthly protection 4 dry circumference
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW091103634A TWI301490B (en) | 2002-02-27 | 2002-02-27 | Catalyst composition and process for preparing norbornene-type homopolymers or copolymers |
| US10/186,977 US6774195B2 (en) | 2002-02-27 | 2002-07-02 | Catalyst composition and process for preparing norbornene-type homopolymers or copolymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW091103634A TWI301490B (en) | 2002-02-27 | 2002-02-27 | Catalyst composition and process for preparing norbornene-type homopolymers or copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TWI301490B true TWI301490B (en) | 2008-10-01 |
Family
ID=27752476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW091103634A TWI301490B (en) | 2002-02-27 | 2002-02-27 | Catalyst composition and process for preparing norbornene-type homopolymers or copolymers |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US6774195B2 (en) |
| TW (1) | TWI301490B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232562B (en) * | 2013-04-08 | 2015-08-05 | 中山大学 | A kind of Cycloolefin addition polymerization catalyst system and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5054589A (en) * | 1973-09-13 | 1975-05-14 | ||
| JPH0463807A (en) * | 1990-03-06 | 1992-02-28 | Idemitsu Kosan Co Ltd | Norbornene polymer, preparation thereof, film prepared therefrom, and preparation of the film |
| US5468819A (en) * | 1993-11-16 | 1995-11-21 | The B.F. Goodrich Company | Process for making polymers containing a norbornene repeating unit by addition polymerization using an organo (nickel or palladium) complex |
-
2002
- 2002-02-27 TW TW091103634A patent/TWI301490B/en not_active IP Right Cessation
- 2002-07-02 US US10/186,977 patent/US6774195B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US6774195B2 (en) | 2004-08-10 |
| US20030162922A1 (en) | 2003-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Photopolymerization of coumarin-containing reversible photoresponsive materials based on wavelength selectivity | |
| Xue et al. | Multicomponent combinatorial polymerization via the Biginelli reaction | |
| Lutz et al. | Synthesis of well-defined alternating copolymers by controlled/living radical polymerization in the presence of Lewis acids | |
| Sehlinger et al. | Tunable polymers obtained from Passerini multicomponent reaction derived acrylate monomers | |
| Jockusch et al. | A steady-state and picosecond pump-probe investigation of the photophysics of an acyl and a bis (acyl) phosphine oxide | |
| Chan et al. | Construction of functional macromolecules with well-defined structures by indium-catalyzed three-component polycoupling of alkynes, aldehydes, and amines | |
| Kingsbury et al. | Regarding the Mechanism of Olefin Metathesis with Sol− Gel-Supported Ru-Based Complexes Bearing a Bidentate Carbene Ligand. Spectroscopic Evidence for Return of the Propagating Ru Carbene | |
| Galan et al. | A rapid and simple cleanup procedure for metathesis reactions | |
| Boffa et al. | “Link-functionalized” polymers: an unusual macromolecular architecture through bifunctional initiation | |
| Cai et al. | Functional isocyanide-based polymers | |
| CN102417454B (en) | Cyclic olefin compound having photoreactive group and photoreactive polymer | |
| Hisano et al. | Sequence-controlled radical polymerization of N-substituted maleimides with 1-methylenebenzocycloalkanes and the characterization of the obtained copolymers with excellent thermal resistance and transparency | |
| Xu et al. | Pyridine N-oxide catalyzed living radical polymerization of methacrylates via halogen bonding catalysis | |
| Matson et al. | Pulsed-addition ring-opening metathesis polymerization: catalyst-economical syntheses of homopolymers and block copolymers | |
| Jakhar et al. | Tethered tungsten-alkylidenes for the synthesis of cyclic polynorbornene via ring expansion metathesis: unprecedented stereoselectivity and trapping of key catalytic intermediates | |
| Stoebenau et al. | Nonchelated d0 Zirconium− Alkoxide− Alkene Complexes | |
| Yu et al. | Difunctional initiators based on 1, 3-diisopropenylbenzene. 3. Synthesis of a pure dilithium adduct and its use as difunctional anionic polymerization initiator | |
| Ebert et al. | Synthesis and Reactivity of Bis (η5: η1-pentafulvene) zirconium Complexes | |
| Kang et al. | Living metathesis and metallotropy polymerization gives conjugated polyenynes from multialkynes: how to design sequence-specific cascades for polymers | |
| Anders et al. | First Controlled Cyclopolymerization of Diethyl Dipropargylmalonate by MoCl5− n-Bu4Sn− EtOH− Quinuclidine and MoOCl4− n-Bu4Sn− EtOH− Quinuclidine To Give Highly Regular Polyenes Consisting Exclusively of 1, 2-(Cyclopent-1-enylene)− Vinylene Units | |
| Frech et al. | Synthesizing Polyethylene from Polyacrylates: A Decarboxylation Approach | |
| Zhang et al. | Incorporation of large cycloalkene rings into alternating copolymers allows control of glass transition and hydrophobicity | |
| TWI301490B (en) | Catalyst composition and process for preparing norbornene-type homopolymers or copolymers | |
| Vela et al. | Solid-state polymerization of aquabis (3-butenoato) calcium | |
| US9081283B2 (en) | Spatial and temporal control of brush formation on surfaces |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK4A | Expiration of patent term of an invention patent |